US3420812A

US3420812A - Disazo dyestuffs metal-complex

Info

Publication number: US3420812A
Application number: US454998A
Authority: US
Inventors: Gerhard Langbein; Fritz Meininger
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1964-05-13
Filing date: 1965-05-11
Publication date: 1969-01-07
Anticipated expiration: 1986-01-07
Also published as: BE663908A; DE1544482A1; DE1544482B2; DE1544482C3; CH451366A; GB1103513A

Description

United States Patent )flice 3,420,812 Patented Jan. 7, 1969 US. Cl. 260148 7 Int. Cl. C09b 45/24; C09b 45/26; C09!) 45/28 Claims ABSTRACT OF THE DISCLOSURE Water-soluble, disazo dyestuffs of the formula and the complex metal compounds of said disazo dyestuffs, wherein Ar is benzene or naphthalene, Ar and Ar;, are benzene, naphthalene, benzene sulfonic acid, naphthalene sulfonic acid, lower alkoxy-benzene, nitrobenzene, nitrobenzene sulfonic acid, lower alkoxy-nitrobenzene sulfonic acid or chlorobenzene sulfonic acid radicals, R is hydrogen or lower alkyl, R is hydrogen or lower alkyl, R is hydrogen, hydroxyl, carboxyl or lower alkoxy, X is sulfonyl or carbonyl, Z is B-chloroethyl, fl-sulfatoethyl, fi-phosphatoethyl or vinyl, n is 1 or 2, the sum of m and m being at least 3, and p stands for 1 or 2, and wherein the groups R in Ar and Ar and OH in Ar are each linked in ortho-position to the adjacent azo group.

The present invention relates to new water-soluble disazo dyestuffs and to their metal complex compounds as well as to a process for preparing them; in particular,

the general formula XZ:\ I n-l m-l HO If the invention relates to water-soluble disazo dyestuffs of Rsiikrz lfi N L R Q 3 E l I N H3CC= --CO-NAr1N=NAr I L R and to the metal complex compounds thereof, i.e., copper,

nickel, cobalt, chromium, manganese and iron complex compounds, wherein Ar, represents a benzene or naphthalene radical containing at least one sulfonic acid group, Ar and Ar represent the same-or different benzene, naphthalene, benzene sulfonic acid, naphthalene sulfonic acid, lower alkoxy-benzene, nitrobenzene, benzene carboxylic acid, nitrobenzene sulfonic acid, lower alkoxy-nitrobenzene sulfonic acid and chlorobenzene sulfonic acid radicals, R represents a hydrogen atom, an aliphatic or araliphatic radical, R represents a hydrogen atom or an alkyl group, R represents a hydrogen atom, a hydroxyl, carboxyl or alkoxy group, X represents a sulfonyl or carbonyl group, Z represents a fl-chloroethyl, fl-sulfatoethyl, B-phosphatoethyl or vinyl group, It stands for 1 or 2 and m and m'each stand for l, 2 or 3, the sum of m+m' being at least 3, and wherein the groups R in Ar and Ar and OH in Ar are each linked in ortho-position to the adjacent azo group.

Now we have found that valuable water-soluble disazo dyestuffs and the metal complex compounds thereof can be obtained by coupling simultaneously or successively 2 mols of the same or different aromatic diazo compounds of which at least one contains at least one group of the formula wherein R represents a hydrogen atom, an aliphatic or araliphatic radical, X represents a sulfonyl or carbonyl group, Y represents a halogen atom, the radical of a polybasic acid or a hydroxyl group, and n stands for 1 or 2, with coupling components of the general formula B2 RlO-A.I"-l IC OCH1C 0-CH:

wherein Ar represents a benzene or naphthalene radical containing at least one sulfonic acid group, R represents a hydrogen atom or an acyl radical and R represents a hydrogen atom or an alkyl group, when using coupling components, in which R, designates an acyl radical, the second mol of the diazo compound is not coupled until the acyl radical has been split off by saponification, whereupon in the disazo dyestuffs obtained, which contain a hydroxyl group in the groups of Formula 1, said alcoholic hydroxyl group is esterified by treatment with polybasic acids, their monoamides or monochlorides, and, if desired, by treating the dyestuffs obtained with agents yielding metal, provided they contain groups forming metal complexes or capable of being converted into such groups.

The disazo dyestuffs obtained which contain groups of Formula 1 can be converted, by treatment with an aqueous alkali, into disazo dyestuffs containing groups of Formula 2. If, however, Y represents a hydroxyl group in Formula 1, the treatment is not carried out until said hydroxyl groups has been esterified.

For the preparation of the novel disazo dyestuffs there may be used, for example, the following diazo compo- 1-hydroxy-7-acetoacetylaminonaphthalene-3-sulfonic acid,

1hydroxy-S-acetoacetylaminonaphthalene-3sulfonic acid,

1 hydroxy 8 acetoacetylaminonaphthalene 3,6 disulfonic acid,

1-hydroxy-3acetoacetylaminobenzene-4-sulfonic acid,

1 hydroxy 7 acetoacetyl N methylaminonaphthalene-3-sulfonic acid or l-(p-toluene-sulfonyloxy)7- acetoacetylaminonaphthalene-3sulfonic acid,

When operating in a weakly acid medium it is possible to couple diazo components having a low coupling energy, such, for example, as ortho-aminophenol derivatives or ortho-aminonaphthol derivatives or 2-arninobenzoic acid,

only once with the coupling components of the above formula, in which R represents a hydrogen atom. In this case, monoazo dyestuffs can be isolated which contain the diazo component linked to the acetoacetylamino group (enolic side). When using diazo components having a higher coupling energy, such as aniline-sulfonic acids or nitroanilines, monoazo dyestuffs can only be prepared if the naphtholic hydroxyl group is previously protected by acylation, for instance with p-toluene-sulfochloride, and resaponified after the coupling. By further coupling with another diazotized amine, advantageously in a neutral or weakly alkaline medium, it is possible to prepare disazo dyestuffs having different diazo components.

As far as the dyestuffs contain groups capable of being metallized, for instance two hydroxy groups or hydroxycarboxy groups in o,o-position to an azo bridge or groups capable of being converted into such groups, said groups can be converted in known manner into metal complex compounds. As agents yielding metal there may be used copper, nickel, cobalt, chromium, manganese or iron compounds. By metallizing the monoazo dyestuffs, coupling them to form disazo dyestuffs and treating them with another agent yielding metal it is also possible to prepare diazo dyestuffs containing different complex-bound metals. A second hydroxy group which is in o-position to an o-hydroxy-azo group can be introduced also by ox ydative coppering.

The new dyestuffs are suitable for dyeing and printing various fibrous materials, such as for example natural or regenerated cellulosic materials, wool, silk or polyamide fibers. They can be fixed on the fibrous material at normal temperature or at an elevated temperature in the presence of agents having an alkaline reaction or yielding alkali in the heat. The dyestuffs obtained according to the process of the present invention are distinguished by a high tinctorial strength, good to excellent light and wet fastness properties and, in many cases, by a good affinity for the fiber when the dyeing is carried out by the exhaust process.

As compared with known dyestuffs of similar constitu tion, for example with those described in German Patent Nos. 870,883, 956,794 and 1,077,812, the new dyestuffs are distinguished by considerably better properties of wet fastness.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight unless otherwise mentioned and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter.

Example 1 217 parts of 1-amino-Z-hydroxybenzene-S-B-hydroxyethyl-sulfone are introduced at room temperature while stirring into 570 parts of concentrated sulfuric acid and stirred for several hours until completely dissolved. The mixture is then poured onto 1,500 parts of ice and diazotized at 510 C. with a solution of 70 parts of sodium nitrite in 110 parts of water. After addition of 1,000 parts of water and 1,500 parts of ice the whole is neutralized by gradually adding the total amount of 1,000 parts of sodium bicarbonate. The temperature is allowed to rise slowly. At 20 C. the formation of foam ceases. 170 parts of the sodium salt of 1-hydroxy-7-acetoacetylamino-naphthalene-3-sulfonic acid are now introduced into the diazotization mixture, the mixture is adjusted to pH 7.5-8.0 by addition of some sodium bicarbonate, heated to 30- 35 C. and stirred for several hours until the coupling is complete. The mixture is then adjusted to a weakly acid pH-value by addition of a 20% hydrochloric acid, the dyestuff salted out by means of potassium chloride and isolated by suction filtration.

The dyestuff which is obtained in the form of a dark brown powder dissolves in water with a red brown color. Its solution changes to red violet upon addition of alkali.

In the form of its free acid the dyestuff corresponds to the following formula 180 parts of the dyestuff which is obtained in a concentration of about 50% are introduced into a solution of 50 parts of crystallized copper sulfate and 110 parts of crystallized sodium acetate in 2,000 parts of water and the whole is heated for 1-2 hours to C. After filtration of the solution the dyestuff is separated by addition of sodium chloride and isolated. It is violet brown powder which dissolves in water with a red brown color and dyes cellulose fibers in the presence of agents having an alkaline reaction red brown shades which are fast to washing and to light. The dyestuff contains 2 copper atoms per molecule.

When using for the metallization, instead of the amount of copper sulfate given above, 30 parts of crystallized cobalt sulfate, a dyestuff is obtained in the form of a blackish brown powder which dissolves in water with a brown color. Prints and padded dyeings prepared with this dyestuff on cotton fabrics show a strong neutral brown having excellent fastness properties to wetting and to light. Valuable brown dyeings and prints are also obtained on polyaniide fibers.

Example 2 189 parts of 1-amino-2-hydroxybenzene-S-sulfonic acid are introduced into 3,800 parts of water and 300 parts of concentrated sulfuric acid, and the whole is then diazotized at 5 10 C. with a solution of 70 parts of sodium nitrite in parts of water. The excessive sodium nitrite is decomposed by addition of some amidosulfonic acid. 345 parts of the sodium salt of 1-hydr0xy-5-acetoacetylamino-naphthalene-3-sulfonic acid are introduced into the mixture obtained in this manner, the pH-value of the mixture is adjusted to about 4.5 by addition of sodium bicarbonate, then 50 parts of crystallized sodium acetate are added and the whole is stirred at room temperature until the coupling is complete. The yellow monoazo dyestuff separated which corresponds to the formula l so H HO N a is filtered with suction and subsequently introduced with stirring into 2,000 parts of water. Then 310 parts of the inner sulfate of 1-diazo-2-hydroxybenzene-S-p-hydroxyethylsulfonyl-sulfuric acid ester are added, the pH-value is adjusted to 7.58.0 by addition of sodium bicarbonate, the whole is heated to 3540 C. and stirred for several hours until the coupling is complete. The dyestuff is precipitated by addition of sodium chloride and then filtered with suction. It constitutes a dark brown powder which dissolves in water with a red brown color. The dyestuff corresponds to the following formula The copper complex dyestuif prepared from the dyestuif obtained in the manner described in Example 1 contains 2 copper atoms per molecule. It constitutes a red brown powder and dissolves in water with a red brown color. With this dyestuif strong red brown dyeings having a good wet fastness and a very good fastness to light are obtained on cellulose fibers in a long bath in the presence of alkalies.

The cobalt complex dyestuff prepared in analogous manner contains only one cobalt atom per molecule and produces prints and padded dyeings having a neutral brown color which is fast to washing and to light.

Example 3 345 parts of the sodium salt of 1-hydroxy-7-acetoacetylaminonaphthalene-3-sulfonic acid are dissolved in 2,500 parts of water. 308 parts of the inner sulfate of 1-diazo-2- hydroxybenzene-S 8 hydroxyethylsulfonyl-sulfuric acid ester are then introduced into this solution While stirring, a 20% sodium acetate solution is dropped in until the mixture shows a pH-value of 3.0, 500 parts of potassium chloride are added and the whole is stirred at about 30 C. until the coupling is complete. The monoazo dyestuflf of the formula I i HON l separates gradually from the solution in the form of a yellow precipitate and is isolated by suction.

25 parts of 1-amino-2-methoxy-4-nitrobenzene-S-sulionic acid are diazotized at 10 C. in a solution of 250 parts of water and 25 parts of concentrated hydrochloric acid by dropwise addition of 17.5 parts of a 40% sodium nitrite solution. The mixture is introduced into a solution of 63 parts of the above monoazo dyestutf in 250 parts of water and 75 parts of anhydrous sodium acetate, and the whole is stirred at room temperature until the coupling is complete. The disazo dyestulf formed which corresponds to the formula is precipitated by addition of potassium chloride. It constitutes a dark brown powder which dissolves with a red color in water.

parts of the dyestuff which is obtained in a concentration of about 50% are introduced into a solution of 25 parts of crystallized copper sulfate and 55 parts of crystallized sodium acetate in 1,000 parts of water and the whole is heated for 2 hours to 80 C. The dyestuff is then precipitated by means of potassium chloride and filtered with suction. It contains 1 copper atom per molecule and constitutes a dark brown powder which dissolves in water with a red brown color. When applied to cotton or polyamide fabrics in the presence of agents having an alkaline reaction the dyestutf obtained produces brown prints having a good fastness to wetting and to light.

Example 4 159 parts of 1-hydroxy-8-aminonaphthalene 3,6 disulfonic acid are neutralized in 1,300 parts of water, while stirring, by addition of anyhdrous sodium carbonate, and completely dissolved. 45 parts of diketene are then dropped in slowly at room temperature and the whole is stirred for some time until no free amino group can be detected any longer.

183 parts of 1-aminobenzene-4-vinylsulfone are diazotized in a solution of 1,000 parts Water and 500 parts by volume of 5 N-hydrochloric acid at 5-10" C. by dropwise addition of parts of a 40% sodium nitrite solution. The diazotization mixture is added to the solution of l-hydroxy-S-acetoacetylaminonaphthalene-3,6-disulfonic acid prepared in the manner described above. Sodium bicarbonate is slowly introduced, with stirring until a pH-value of 6.5-7.0 is obtained, and the whole is stirred until the coupling is complete. The disazo dyestuif formed is salted out with potassium chloride and filtered with suction. It constitutes a dark red powder, dissolves in water with a red color and corresponds to the following formula When applied to cellulose or polyamide fibers or wool in the presence of agents having an alkaline reaction the dyestuff yields dark red dyeings or prints having excellent wet fastness properties and a medium fastness to light.

Example 5 217 parts of a 1-amino-2-hydroxybenzene-S-B-hydroxyethylsulfone are converted into the sulfuric acid ester in the manner described in Example 1 and diazotized. A solution of l-hydroxy 8 acetoacetylaminonaphthalene- 3,6-disulfonic acid prepared as described in Example 4 is added to the neutralized diazotization mixture. The pH- value of the mixture is adjusted to 7.5-8.0 by addition of sodium bicarbonate and maintained at this value. The mixture is heated to 3035 C. and stirred until the coupling is complete. The dyestufl? is precipitated by acidification with hydrochloric acid and addition of potassium chloride and isolated. It constitutes a dark powder and dissolves in water with a yellow red color. The color of the solution changes to red violet upon addition of alkali. The dyestulf corresponds to the following formula 170 parts of the dyestuif which is obtained in a concentration of about 60% and heated to the boil within 3 hours in 750 parts of water containing 26 parts of chromium triacetate. The reaction mixture is then evaporated to dryness in vacuo. The dyestuff which is obtained in the form of a black powder dissolves in water with a greyish-green color. The prints obtained on cotton or staple fiber fabrics have a strong olive green color of excellent fastness properties to Wetting and light.

Example 6 170 parts of the sodium salt of l-hydroxy-7acetoacetylamino-naphthalene-3-sulfonic acid are dissolved in 2,000 parts of water and 230 parts of the diazoxide of l-amino- 2-hydroxy-benzene-5-fi-hydroxyethylsulfone are added with stirring. The pH-value of the mixture is adjusted to 12.0 by dropwise addition of sodium hydroxide solution of 380 B. and the whole is stirred for several hours at room temperature until the coupling is complete. By dropwise addition of a hydrochloric acid the mixture is then adjusted so as to show a weakly acid reaction to Congo paper and stirred until thinly liquid. The product is then filtered with suction, washed with a small amount of dilute hydrochloric acid and dried. In its present form the dyestutf is only sparingly soluble in water, but dissolves with a red brown color upon addition of alkali. It corresponds to the following formula SO2-CHz-CHz-OH 200 parts of said dyestuff are introduced slowly and with stirring into 1,000 parts of concentrated sulfuric acid. The whole is stirred for several hours at 30 C. until the dyestutf has completely dissolved. The mixture is then poured on 3,000 parts of ice while stirring is continued and the dyestufi is salted out by addition of 800 parts of sodium chloride. After filtration by suction the filter cake which still shows a strongly acid reaction is once more suspended with saturated sodium chloride solution, neutralized by careful addition of sodium bicarbonate and again filtered with suction.

The dyestuff which is obtained in the form of a dark brown powder is identical with that described in Example l and may likewise be converted into metal complex compounds.

Example 7 345 parts of the sodium salt of l-hydroxy-7-acetoacetylamino-naphthalene-3-sulfonic acid are dissolved in 4,000

parts of water, and 30 parts of glacial acetic acid are added. Subsequently 228 parts of the diazoxide of 1- amino-Z-hydroxy-benzene-S-fi-hydroxyethylsulfone are introduced with stirring, and the whole is stirred for several hours at room temperature until the coupling is complete. The monoazo dyestuff which is obtained in the form of a yellow precipitate is filtered with suction, washed with a 5% sodium chloride solution and dried. It corresponds to the following formula parts of the dyestulf which is obtained in a concentration of about 70% are introduced into 300 parts of anhydrous pyridine and, after addition of 5 parts of urea, heated to C. At this temperature 35 parts of amidosulfonic acid are gradually introduced and the whole is then heated for about 1 hour to -105 C. After cooling the mixture is poured into 2,500 parts of water, a 20% hydrochloric acid is added until the mixture shows a weakly acid reaction to Congo paper, the precipitation of the dyestufl? is completed by introduction of 200 parts of sodium chloride and the dyestutf is filtered with suction.

The sulfuric acid ester of the monoazo dyestuff which is obtained in the form of a yellow powder is identical with the monoazo dyestuff described in Example 3. By further coupling with any diazotized aromatic amines desired disazo dyestuffs can be prepared in the manner described in Example 3.

The esterification in pyridine may be effected in analogous manner with the aid of chlorosulfonic acid at a temperature between 30 and 40 C.

Example 8 100 parts of the monoazo dyestuff described in Example 3 which is obtained in a concentration of about 60%, are introduced into a solution of 25 parts of crystallized copper sulfate and 55 parts of crystallized sodium acetate in 800 parts of water and stirred for 1 hour at 80 C. After cooling the copper complex dyestuff formed is salted out by means of potassium chloride, filtered with suction and washed with saturated potassium chloride solution. The moist dyestnff paste is then introduced into 500 parts of water, and 31 parts of the inner sulfate of 1 amino-Z-hydroxybenzene-5-5-hydroxyethylsulfonyl-sulfuric acid ester are added. The pH-value of the mixture is adjusted to 7.5-8.0 by addition of some sodium bicarbonate and the Whole is stirred at 35 C. until the coupling is complete. The dyestutf which has been precipitated with potassium chloride and isolated is obtained. in the form of a dark brown powder. It dissolves in water with a red brown color and corresponds to the following formula 100 parts of said dyestuff which is obtained in a strength of about 50% are stirred up for 1 hour at 80 C. in 500 parts of water containing parts of cobalt acetate. After cooling the dyestufl is precipitated with potassium chloride and filtered with suction. The dyestulf which is obtained in the form of a dark brown powder dissolves in water with a red brown color and, when applied tocotton or staple fiber fabrics, produces strong brown prints or dyeings showing excellent fastness properties to light and wet processing. 2 dyestufi molecules contain together 2 copper atoms and 1 cobalt atom.

Example 9 320 parts of 1-hydroxy-7-acetoacetylamino-naphthalene- 3-sulfonic acid are dissolved in 3,000 parts of water.

While stirring 644 parts of the inner sulfate of 1-diazo-2- SOz-CHz-CH2OSOH 160 parts of the dyestuff which is obtained in a strength of about 60% are heated to the boil for about hours, in 1,000 parts of water containing 60 parts of crystallized copper sulfate, 70 parts of crystallized sodium acetate and parts of glacial acetic acid. After cooling the dyestufi is salted out by means of potassium chloride and filtered with suction. The dyestuif obtained contains 2 copper atoms per molecule and has the same properties and composition as the copper complex dyestuff described in Example 1.

Example 10 189 parts of 1 amino 2 hydroxybenzene 5 sulfonic acid are introduced into a solution of 3,800 parts of water and 300 parts of concentrated hydrochloric acid and diazotized at 5l0 C. with 175 parts of a sodium nitrite solution. 345 parts of the sodium salt of 1 hydroxy 7 acetoacetylamino-naphthalene 3 sulfonic acid are introduced into this mixture, the pH-value is adjusted to 4.5 by addition of sodium bicarbonate, parts of crystallized sodium acetate are added 'and the whole is stirred at room temperature until the coupling is complete. The yellow monoazo dyestufi precipitates during the operation. 295 parts of the inner salt of 1- diazobenzene 4 B hydroxyethylsulfonyl sulfonic acid ester are then added, the pH-value is adjusted to 6.06.5 by addition of sodium bicarbonate and the whole is stirred at room temperature until the coupling is complete. The mixture is then adjusted with hydrochloric acid to a pH-value in a weakly acid range, the disazo dyestulf is precipitated by addition of potassium chloride and filtered with suction. The dyestuff which is obtained in the form of a red brown powder dissolves in water .with a red brown color and dyes cotton orange brown shades. It corresponds to the following formula 135 parts of said dyestulf which is obtained in a strength of about 60% are introduced into a solution of 56 parts of crystallized copper sulfate and 60 parts of crystallized sodium acetate in 1,000 parts of water. The pH-value of the mixture is adjusted to 5.5-6.0 by addition of a small amount of anhydrous sodium carbonate. 50 parts of a 15% hydrogen peroxide are dropped into this solution within 2 hours at 1520 C., and the whole is stirred for some time at room temperature. The dyestuff which has been precipitated by means of potassium chloride and isolated constitutes a brown powder which dissolves in water with a red brown color. The dyestuif corresponds to the following formula In the presence of agents having an alkaline reaction red brown dyeings and prints of good fastness properties to light and wetting are obtained on cotton and staple fibers.

Example 11 520 parts of the sodium salt of 1 (p toluene-sulfonyloxy) 7 acetoacetylamino naphthalene 3 sulfonic acid are suspended in 2,500 parts of Water. 230 parts of the inner sulfate of 1 diazo 2 nitrobenzene- 4-sulfonic acid are introduced while stirring, parts of anhydrous sodium acetate are added and the whole is stirred until the coupling is complete. By addition of a small amount of sodium chloride the monoazo dyestufi precipitates from the solution which has an intense yellow. color in the form of lemon yellow flakes. The dyestuif is separated from excessive diazonium salt by suction, the moist filter cake is dissolved in 5,000 parts of water, 1,000 parts by volume of sodium hydroxide solution of 38 B. are added and the whole is heated for a r 11 short period of time to 90 C. After cooling the whole is neutralized by means of concentrated hydrochloric acid, 310 parts of the inner sulfate of l diazo 2 hydroxybenzene 5 B hydroxyethylsulfonyl sulfuric acid esterare added while stirring, the pH-value of the mixture is adjusted to 7.5-8.0 by addition of sodium bicarbonate and the whole is stirred at 30-35 C. until the coupling is complete.

The disazo dyestutf formed is precipitated with potassium chloride and filtered with suction. It constitutes a dark brown powder which dissolves in water with a red browncolor. The dyestuff corresponds to the following formula OaN [I OH HO N l 170 parts of the dyestuff which is obtained in a concentration of about 50% are introduced into a solution of 25 parts of crystallized copper sulfate and 55 parts of crystallized sodium acetate in 1,000 parts of water and the whole is heated for 1 hour to 80 C. The dyestuft is precipitated by means of sodium chloride and filtered with suction. It constitutes a dark brown powder which dissolves in water with a red brown color. With the use of this dyestulr claret dyeings and prints having a good fastness to light and to wet processing are obtained on cellulose fibers.

Example 12 312 parts of 1-amino-2-hydroxy-5-(N-ethionyl-N-methylamino)-benzene are diazotized at 5l0 C. in a solution of 2,000 parts of water and 250 parts of concentrated hydrochloric acid by dropwise addition of a solution of 70 parts of sodium nitrite in 110 parts of water. Excessive sodium nitrite is decomposed by addition of a small amount of urea. 170 parts of the sodium salt of l-hydroxy- 7-acetoacetylamino-naphthalene-3-sulfonic acid are then introduced into the mixture, the pH-value is adjusted to 7.5 by addition of sodium bicarbonate and the whole is stirred for several hours at room temperature until the coupling is complete. The dyestutf which has been precipi tated by addition of potassium chloride and isolated constitutes a dark brown powder which dissolves in water with a brown color. In the form of its free acid it corresponds to the following formula The copper complex dyestutf prepared from the above dyestufl in the manner described in Example 1 contains 2 copper atoms per molecule. The dyestulf constitutes a brown powder which dissolves in water with a red brown color. When applied to cotton .or staple fibers in the presence of agents having an alkaline reaction the dyestuff yields red brown dyeings and prints having an excellent fastness to light and washing.

The corresponding cobalt complex dyestufr' contains only 1 cobalt atom per molecule and yields neutral brown prints.

Example 13 170 parts of the sodium salt of l-hydroxy-S-acetoacetylamino-naphthalene-3-sulfonic acid are dissolved in 1,700 parts of water. 295 parts of the inner sulfate of 4 ([3 chloropropionylamino)-l-diazobenzene-2-sulfonic acid are introduced while stirring, the pH-value of the mixture is adjusted to the point of neutrality by addition of some sodium bicarbonate and the whole is stirred until the coupling is complete. The dyestutf which has precipitated in the form of crystals is filtered with suction. It

constitutes a dark red powder and corresponds to the following formula The dystuff dissolves in water with a yellowish-red color. On cellulose fabrics it produces red prints and padded dyeings having excellent properties of wet fastness.

Example 14 63 parts of the monoazo dyestuff obtained as described in Example 3 are introduced into 600 parts of water, and 26 parts of the inner sulfonate of 5-acroy1amino-1-diazobenzene-Z-sulfonic acid are added while stirring. The pH- value of the mixture is maintained at 7.07.5 by addition of some sodium bicarbonate, and the whole is stirred for several hours until the coupling is complete.

The dyestuff is precipitated with potassium chloride and filtered with suction. It is obtained in the form of a dark brown powder, which dissolves in water with a yellowishbrown color. The dyestuff corresponds to the following formula H SOaH HO N 177 parts of the dyestuff which is obtained in a concentration of about 50% are introduced into a solution of 25 parts of crystallized copper sulfate and 55 parts of crystallized sodium acetate in 1,500 parts of water and the Whole is heated for 1-2 hours to 80 C. After cooling the dyestuff is salted out by addition of sodium chloride.

water with a yellowish-brown color. The dyestuff contains 1 copper atom per molecule. On cotton and polyamide fibers the dyestuff yields clear brown shades having a good fastness to light and to washing.

Example 15 170 parts of the metal-free dyestulf prepared as described in Example 5 and having a purity of about 60% are dissolved in 900 parts of water. Within 1 hour 60 parts of sodium hydroxide solution of 38 B are dropped in at room temperature while stirring and stirring is continued for some time. The mixture is then neutralized by dropwise addition of a 20% hydrochloric acid, the vinylsulfone dyestuff formed is salted out by addition of 100 parts of sodium chloride and isolated by suction filtration. The dyestuff constitutes a dark brown powder and dissolves in water with the same color as the starting dyestulf but is more sparingly soluble than the latter. The dyestufi corresponds to the following formula 135 parts of the dyestuff which is obtained in a strength of about 60% are heated for about 1 hour to 80 C. in 750 parts of water containing 15 parts of cobalt acetate. After cooling 250 parts of sodium chloride are added, thus causing the precipitation of a dyestufi containing only 1 cobalt atom per 2 dyestufi molecules. The dyestuff which is obtained in the form of a blackish brown powder dissolves in water with a dark red brown color. The prints obtained on cotton or staple fiber fabrics show a strong dark brown shade having an excellent fastness to light and to washing.

Example 16 189 parts of 1-amino-2-hydroxybenzene-S-sulfonic acid are diazotized in the manner described in Example 2. 345 parts of the sodium salt of l-hydroxy-7-acetoacetylaminonaphthalene-3-sulfonic acid are introduced into the mixture obtained in this manner, the pH-value is adjusted to 4.0 by addition of sodium bicarbonate, 100 parts of crystallized sodium acetate are added and the whole is stirred for several hours until the coupling is complete. In the course of this operation the yellow monoazo dyestuff formed precipitates partially. Then 230 parts of the diazoxide of 1-amino-2-hydroxybenzene-S-B-hydroxyethylsulfone are added, the pH-value of the mixture is adjusted to 9.0-9.5 by addition of anhydrous sodium carbonate and the whole is stirred for several hours at room temperature until the second coupling is complete. The mixture is then adjusted to a pH-value in a weakly acid range by dropwise addition of a 20% hydrochloric acid, and the precipitation of the disazo dyestuff is completed by addition of sodium chloride. The dyestulf which is obtained in the form of a dark red powder dissolves in water with a red color, and upon addition of alkali the solution changes to dark red with a'greyish-green dichroism. The dyestutf corresponds to the following formula 125 parts of said dyestulf which is obtained in a concentration of about 60% are slowly introduced into 625 parts of concentrated sulfuric acid while stirring. Stirring is continued for several hours at room temperature until the dyestulf has completely dissolved. Subsequently, the mixture is poured onto 1,900 parts of ice while stirring, the esterified dyestuff is salted out by addition of sodium chloride, filtered with suction and washed with saturated sodium chloride solution. The moist filter cake is then dissolved in 1,000 parts of water and neutralized with some sodium hydroxide solution. Within about 30 minutes 50 parts of a 36% potassium hydroxide solution are dropped in at room temperature and the whole is stirred parts of the dyestuff which is obtained in a concentration of about 60% are converted into the cobalt complex in the manner described in Example 15. During the operation a dyestulf precipitates which contains 1 co balt atom per 2 dyestuif molecules. The dyestufi is obtained in the form of a blackish brown powder and dissolves in water with a brown color. The prints and padded dyeings obtained on cotton or staple fiber fabric show a neutral brown color of an excellent fastness to light and to washing.

The corresponding chromium complex dyestutf containing l chromium atom per dyestulf molecule yields blackish-brown shades having likewise excellent fastness properties.

The dyestuffs specified in the following table can be prepared in analogous manner. They also yield dyeings and prints of good fastness properties.

Diazo components Coupling component Metal Tint I. Enolic side II. Naphtholic side l-amino-2-hydroxybenzene-5-fl-hydroxy- 1-amino-2-hydroxybenzene-Hi-hydroxyl-hydroxy-7-acetoacetylaminonaph- Cr Blackishethylsulionylsulfuric acid ester. thalene-B-suiionic acid. brown.

0 dn Ni Red brown. l-amino-2-hydroxybenzene-5-sulfonic acid Do. Neutral brown. 1-amino-2-hydroxy-3-chlorobenzene-5- -do do Go Do.

sulfonic acid. l-amino-2-hydroxybenze11e-5sulionic acid. l-amino-benzene-4-B-hydroxyethyl- -..do Cu Clear redsulfonyl-sulfuric acid ester. V brown. Do do do Co Yellowish brown. Do l-aminobenzene-3-B-chloroethylsulfone do Cu Red brown. 1-amino-2-hydroxybenzene-S-B-hydroxyl-aminobenzeue-i-sulfonic acid -do Cu Do ethyisulfonylsuliuric acid ester.

Do do ..do 00 Brown. Do l-an 31o-2-hydroxybenzene-5-sulionic .do Cu Red brown.

aci Do do dn Co Neutral brown. Do l-aminonaphthaleue-4-sulfonic acid .do Cu Red brown. 1-amin0-2-hydroxybenzenei-fl-hydroxyl-amino-2-hydroxybenzene-M9-hydr0xy- -do Cu Do ethylsuhonylsulfurie acid ester. ethylsulionyisuliuric acid ester;

Do do .do Co Neutral brown. Do d Cr Blackish brown. l-amino-2-hydr0xybenzene-5-sulfonic acid dn Cu Violet-tinged rown. Do do do Co Greyish brown. Do do -.do Or Blackish brown. l aminobenzene-d-B-hydroxyethylsull-amino-benzene-4-5-hydroxyethylsuldo Claret.

fonylsulfuric acid ester. fouylsuliuric acid ester. l-amino-2-hydroxybenzene-fi-fi-hydroxyl-aminobenzene-2-carboxylic acid-4.- .do Cu Red brown.

ethylsulfonylsuliuric acid ester. sulfonic acid.

Do- .do ..do Co Yellowish brown. Do Or Neutral brown. 1-aminobenzene-2-carboxylic acid-5- 1-aminobenzene-2-carboxylic acid-E-fl- -do Cu Red brown.

hydroxyethylsulionyl-suliuric acid hydroxyethylsulionyl-suliuric acid ester. ester.

Do d 00 Brown. Do .d0 Red brown. l-amino-z-nitrobenzene-sulionic acid..... 1-aminobenzene--fl-hydroxyethylsul- Do.

fonyl-sulfuric acid ester. D0 1-amino-2-hydroxybenzene-S-fl-hydroxy- .do Cu Claret.

ethylsulfonyl-suliuric acid ester. D do -do Co Violetish red brown. l-aminobenzene-Z-carboxylic acid -do 1-hydroxy-B-acetoacetylamino-uaph- Cu Red brown.

thalene-B-sulfonic acid. Do. Brown. Claret. Reddish brown. l-hydroxy-5-acetoacety1amino-naph- Cu Red brown.

thalene-3-sulfonic acid. Co Neutral brown. Yellowish ionyl-suliuric acid ester. brown. o Brown. Do l-aminobenzene-ifl-hydroxyethylsul- D ionyl-phosphoric acid ester. l-aminobenzene-3-fl-hydroxyethyisul- 1-aminobenzene-3-B-hydroxyethylsul- Scarlet.

fonyi-sulfuric acid ester. fonyl-sulfuric acid ester. 1-amino-2-hydroxybenzene-fi-B-hydroxy- 1-amino-2-hydroxybenzene-fi-B-hydroxy- 1-hydroxy-7-(acetoacetyl-N-methyl- Cu Red brown.

ethylsulionyl-suifuric acid ester. ethylsulionyl-sulfuric acid ester. amino)-naphtha1ene-3-sulionic acid.

Dn do 7 Co Reddish dark brown. do Cr Bluish brown. 1-hydroxy-7-acetoacetylamino-nap h- Cu Red brown.

thalene-3,6-disulfonic acid.

do Co Neutral brown. Dn rin do Gr Greyish brown. D dn 1 hydroxy-S-acetoacetylamino-naph- Cu Violet-tinged thalene-5-suliom'c acid. dark brown.

Do Do. l-amino-2-hydroxybenzene-S-B-hydroxyl-amino-2-hydroxybenzene-5-B-h hydroxy toacetylamino-naph- Cu D0.

ethylsulionyl-suliuric acid ester. ethylsulfonyl-suliuric acid ester. tha1eue-3,6-disu1ionic acid.

Dn fin an Co Blackish brown. 3,, (in (in Ruby red. Do "d do Claret. Dn d .do-..- Yellowish brown. l-amino-2-hydroxynaphthalene-4-suldo Violet-tinged fonic acid. rown.

Do do Violetish red brown. Do do ..d0 Cr Grey. l-amino-2-hydr0Xy-3-nitrobenzene-5-B- l-amino-2-hydroxy-3-nitrobenzene-5-fi- ...do Cu Violetish red h zdroxyethylsulicnyl-suliuric acid h adroxyethylsulionyl-sulfuric acid brown. es er. es er.

Do do .J Co Violet-tinged grey. l-aminobenzene-iifl-hydroxyethylsull-amincbenzene-3-fl-hydroxyethylsuln Scarlet.

i'onylphosphoric acid ester. fonyl-phosphoric acid ester. 1-aminobenzene-3-fl-chloroethyisulfone 1-aminobenzene-3-B-chloroethylsuli'one .do Do. l-amino-2,5-dimethoxybenzene-ivinyl- 1-amino-2,5-dimethoxybenzene-4-vinyl- -do Ruby red.

sulioue. fone.

Diazo components Coupling component Metal Tint I: Enolic side 11. Naphtholic side I-amino-Z-hydroxybenzene-B-B-hydroxyl-amino-Z-hydroxybenzene--fl-hydroxyl-hydroxy-8-acetoacetylamino-naph- On Bed brown.

ethylsulionyl-sulfuric acid ester. ethylsulfonyl-suliuric acid ester. tha1ene-3,5-disu1fonic acid.

D do do 00 Dark brown. D do..-...- .d0 Or Greyish brown. D 1-hydroxy-3-aeetoacetylaminobenzene-i- Cu Red brown.

sulfonic acid. Do do ..d0 Go Do; l-amino-2-hydroxybenzene-5-su1fonic acid. 1-arnino-4-(N-methyl-N-ethionyl)- 1-hydroxy-7-acetoacetylamino-naph- Cu Do.

aminobenzene. thalene-3-sulfonie acid. Do ..do Cr Turbid red. Do.-. l-amino-de(N-methyl-N-vinylsuifonyh- Red brown.

aminobenzene. Do 1-amino-4-acroy1aminobenzene do Cu Do. Do do (in Do, Do l-amino-2-methoxy-x-B-chloropropionyl- .do Do.

benzene (obtained by reaction of 1- arnino-Z-methoxybenzene with B- ohloropropionylchloride according to Friedel-Craits). 1-amino-2hydroxybenzene-5-fl-hydroxy- 1-amino-4-B-hydroxyproplonylamino- '-....do Cu Do.

ethylsuiionylsuliuric acid ester. benzene-sulfuric acid ester. 1-amino-4-(N -methyl-N-fi-ch1oroethyll-amino14-(N-methyl-N-fl-chloroethyll-hydroxy-S-acetoacetylamiuo-naph- Dark red.

sulfonyD-aminobenzene. sulfonyl)-aminobenzene. tha1ene-3,6-disuiionic acid.

We claim: 2. The complex chromium compound of the dyestuff 1. Water-soluble dlSaZO dyestufi of the formula of the formula SOz-CHz-CHz-O-SOaH R;Ar1 N XZ I H OH OH L so Ho N i N 11-1 1 I i ll o= C-CO-NH N=N HO N OH R: H3C=-C ONAI1N=NA.I3E N X-Z SOgH L k (S z )n n-l w-r SO:CHz-CH2O- Oa 3. The compleir copper compound of the dyestutf of the formula SO3H or a complex metal compound thereof containing a metal 40 R of the group consisting of copper, cobalt, nickel, chro- 110- mium, manganese and iron, wherein Ar represents a member selected from the group consisting of benzene N and naphthalene; Ar and Ar represent members selected H0 'l SOZH from the group consisting of benzene, naphthalene, benzene sulfonic acid, naphthalene sulfonic acid, lower alk- EXPO-C43 0-NH SOF'CHT'CHPO BOQH oxy-benzenes, nitrobenzenes, nitrobenzene sulfonic acid, 4. The complex chromium compound of the dyestufi of lower alkoxy-nitrobenzene sulfonic acid and chlorobenthe formula zene sulfonic acid radicals, R represents a member selected from the group consisting of hydrogen and lower alkyl, R represents a member selected from the group consisting of hydrogen and lower alkyl, R represents a member selected from the group consisting of hydrogen, hydroxyl, carboxyl and lower alkoxy; X represents a member selected from the group consisting of sultonyl H0 1i SOr-CHz-CHr-O-SOaH and carbonyl, Z represents a member selected from the L NH 0H OH group consisting of 13-chloroethyl, B-sulfatoethyl, fi-phos- I phatoethyl and vinyl, 1: stands for one of the integers 1 and 2, m and m stand for one of the integers 1 and 2 the sum of mand m being at least 3, and p stands for E03 S03]; one of the integers 1 and 2, and wherein the groups R in Ar and Ar and -OH in Ar; are each linked in orthoposition to the adjacent azo group. 5. The dyestufi of the formula SOBH 0 l l -l| A) N 0 Cu--0 l i Haoi:=o-co-NH N= =N SOaH -S0:CH:CH2

6. The complex copper compound of the dycstuff of the formula 7. The complex cobalt compound of the dyestulf of 20 the formula I SOaGH=CH:

I HO

1103s son;

References Cited UNITED STATES PATENTS FLOYD D. HIGEL, Primary Examiner.

US. Cl. X.R.